Process for treatment of hydrocarbons



Patented Aug. `8, 1944 raocEss Foa TREATMENT or nrnvaocaaaons eorge G. OberfellfBal-tlesvillc, Okla., assigner to Phillips Petroleum Company, a corporation of Delaware Application August 12, 1940, Serial No. 352,306

6 Claims.

This invention relates to a process for the separation and concentration of dioleflnic hydrocarbons such as butadiene and the like from mixtures containing other hydrocarbons. More particularly it refers to the separation of diolefins by a process in which said dioleiins are succes- 1 sively converted to polymers ofrelatively low molecular weight, separated in polymer form by distillation or other suitable methods, and finally recovered as monomeric dioleilns by a depolymerization treatment. An object of this invention is to separate dioleiins from mixtures containing other hydrocarbons such as parailins and monoleflns.

Another object of this invention is to produce diolefins in concentrated' form suitable for use in chemical conversion processes.

,Another object of this invention is to freeof diolefins hydrocarbon mixtures such as are produced by cracking operations.

The manufacture of butadiene, isoprene, and similar conjugated diolens from petroleum hydrocarbons by cracking, dehydrogenation, and

` similar methods is handicapped by the fact that the desired dioleiin generally is obtained in a very dilute form. in admixture with other hydrocarbons. For example, the four-carbon-atom fraction of gases from vapor phase oil cracking stills will usually containless than 15 to 20 per cent of butadiene. Pyrolysis of butane gas under conventional conditions likewise gives very low percentages of butadiene. As a rule, a similar fraction from other cracking processes will contain much smaller percentages of butadiene.

In commercial processes utilizing dioleflns lit is (cl. 26o-681.5) Y i depolymerization to yield the original dioleflns rather than cracking toform lower hydrocarbons, hydrogen, aromatica-etc.

Diolens, such as butadiene and isoprene, undergo two distinct types of polymerization; one leads to the lformation of dimers of a' cyclic nature and the other to the formation of more or less rubbery polymers of .high molecular weight and open branched or unbranched chain structure. 'Ihe formation of the higher polymers is generally favored by low temperatures, such as i 20o-300 F. or lower, and by polymerization catalysts, such as oxygen, peroxides and other active oxygen containing compounds, alkali metals, acids, and metal halides. In general Ithese are either catalysts or chemicals which rex act with the diolefln to form addition complexes.

tivel to have said diolefins in concentrated form. I

For example, in the conversion of butadiene to synthetic rubber by copolymerization with unsaturated nitriles and other costly organic decontaining said dlolen in a dilute form by poly-A merizing the dioleiln under conditions favoring the formation of low polymers, preferably the dimer, then separating the polymers from the unpolymerized hydi'ocarbe'tms by suitable means. such as fractional distillation, and then treating I propose to carry out the polymerization of dioleiins under conditions which favor the formaoperate in the temperature range 30G-900 F.'

The rate of reaction of course increases with the temperature. Elevated pressures are generally advantageous and I have found that pressures 'within the range of atmospheric to around 500 pounds perl square inch gauge are particularly effective. be employed where desirable, limited only by the 'degree of polymerization of the dioleiin. Solid contact catalysts such as fullers earth, bauxite, activated alumina, and silica gel favor the formation of the dimer in both liquid and vapor phase. It is also frequently advantageous to use inhibitors which repress the formation of the higher polymers, particularly in the lower part of the temperature range specified above.

While I may apply my invention directly to hydrocarbon fractions of comparatively wide boiling range, I prefer to separate fractions of rather narrow distillation range containing the desired diolefln and then subject the said frac--l tions to the polymerization treatment.v For example, I may separate a fraction boiling from 15 to 30 F. containing butadiene and `a fraction boiling from to 105 F. containing isoprene for treatment by my process.

Since the dimers which I form in my 'poly-f the low vpolymers under conditions which favor uA method of separation. The separation ofthe Higher pressures, however, may

` peratures of 900 to 1300 F. are preferred, but

v the higher temperatures.

considerably higher temperatures may be used providing the heating time is made suiliciently short to limit ordinary thermal decomposition. In general, shorter heating times are desirable at It is advantageous in many cases to limit theextent of conversion per pass in this manner and to separate and recycle the unconfverted,l polymer in order to obtain higher yields of the monomeric diolen.

As an alternative vto the use of very low pres: sures I may dilute the polymers with an inert gas such as nitrogen, or with steam. The main object is yto maintain a low partial pressure of dimer, and consequently of the monomeric dioleiin, in the reactor.

The use of catalysts such as silver, copper, platinum, iron preferably in the form of the' reduced oxides, and oxides of calcium and mage nesium -in the depolymerization step may also be advantageous. The optimum conditions of temperature and ow rate foriany given catalyst may be determined by simple experiment;

The voperation of the proce s is illustrated by the flow diagrams of Figures 1 and 2. In Figure l a raw petroleum or natural gas fraction such 'as a Cz-I-Ca fraction enters through pipe I0 to cracking coil II heated by furnace I2 where it is cracked to a suitably limited degree. The products leaving vthe, cracking coil are suitably cooled and then passed intofractionating system I3 which may consist of one or, preferably, two or three fractionating columns. A C4 fraction vis removed from fractionating system I3, through drocarbons are withdrawn from fractionating system 2| through pipe 22 and may be wholly or in part recycled to polymerization coil I8 or they may be completely discharged. The oily polymer is depolymerized in coil 24 heated by furnace 25 and maintained at a suitably low pressure by pump-compressor 25. 'I-he products are treated.

' in the fractionating system 21 consisting of one or more columns. A Ci fraction rich in butaascaaoa coil 46. heated-by furnace 41. Lower and higher boiling fractions are withdrawn from the fractionatingsystem 4|,.through pipes 42 and 44, respectively. Products from the polymerization coil 45 after suitable cooling are fractionated in fractionator 49 anda normally liquid polymer is withdrawn through expansion valve 80 and pipe I to depolymerization coil 52 heated ins furnace diene is removed from pipe 29, a fraction com 53. Unpolymerized lig'ht hydrocarbons are withdrawn from fractionator 49 by means of pipe 50 and may be either discharged, or fractionated and partially recycled to the polymerization coil 46. The products from the depolymerization coil 52 are pumped through pipe 54 by means of pump compressor 55 to fractionating system 5B, from which a C4 fraction rich in butadiene is removed through pipe 58. A more volatile fraction which may be produced by partial cracking is with- 'drawn from pipe 51. A normally liquid fraction is withdrawn through pipe 59- and may be recycled as a whole or fractionated to eliminate very heavy materials and the lighter fraction recycled. f

The flow diagrams show only the essential apparatus. In actual operation many modifications may be advantageous. For example, heat exchange between the products and the raw feed' of each of the furnaces may be applied. Greater flexibility in operation and control may be' effected by inserting accumulators between stages of the process. Some of the fractionating system shown as single columns would actually comprise two or possibly three columns with the usual auxiliary and control equipment.l Suitable catalysts may be used in polymerization coils I8 and 46 and depolymerization coils 24 and 52. Other suitable equipment and modifications will be obvious to those skilled in the art.

Although the flow diagrams indicate continuous processes, my invention may obviously be applied as abatch process as well. The following examples include two methods of practicing my invention.

Example 1.-An ethane-propane mixture is cracked at one atmosphere pressure and 1450 F. temperature deeply enough to form 5 per cent of C4 and heavier hydrocarbons. A C4 fraction is separated having `the following composition.

Per cent Butnes, PAT-fm 10 Butadiene, FAHR 50 -rsobucyna 04H '3o Normal butenes, CiHs 10 irate that 20 percent per pass is converted into vgaseous products. The saidgaseous products are separated and a C4 fraction is cut therefrom which is found to be concentrated butadiene.

c Liquids boiling at 2o to 450 r'.v are recycled to the depolylnerization furnace.

Example 2.-A C4 fraction of the vapors produced in a vapor phase oil cracking process are digestedvat 390 F. and 500 pounds per square inch gauge pressure suiliciently to convert 15 to 20perl cent of the total into normally liquid hychain dioleiin.

drocarbons. These polymeric liquid hydrocarbons are separated by fractionation and are then passed at atmospheric pressure through a tube lled with bauxite at 93011'. at such a rate that 20 per cent per pass is converted into gaseous products. The said gaseous products are sepature andv in themaintain low partial pressure of the dimer which which comprises subjecting the hydrocarbon mix- V ture in a polymerization step to conditions of elevated temperaturel and superatmospheric pressure which promote dimerization of said diol'eiin to the dimer thereof as the rincipal reaction occurring, separating the resisting dimer from the eiliuent of the .polymerization step. and subiecting the dimer in a depolyinerization step to conditions of'eievated temperatures and in the presence of sumcient steam to maintain low partial pressure of said dimer electing conversion of said dimer to the monomeric low-boiling open 2. The processor claim i in which butadiene lathe low-boiling open chain diolen.

3. The process for the separatign'of a lowboiling open chain diolen from a mixture of hydrocarbons having boilingpoints within about 15 F. of the boiling 'point of the dioiedn which comprises polymerizing the diolenn in the presence of said hydrocarbons in a polymerization step under conditions of elevated temperature and superatmospheric' pressure which promote as the principal reaction dimerization of the diy oleiin to the dimer thereof having a boiling point appreciably greater than that of the diolefin. fractionating the eilluent oi' the. polymerization step to separate the dimer therefrom. depolymerisingatleastapartofthedimerinthe eiiluent of the; polymerization step in a depoly-` oxide depolymerisation catalyst electing depolyprincipal reaction merizationy step to conditions of elevated temperapresence ofbsuiilcient steam to promote depolymerization ofthe dimer to the monomeric diolefin, fracticnating the eilluefnt of the depolymsrization step to separate the dioiefin from the dimer, and depolymerization sten Y 4. The process for the separation of butadiene from a mixture of C4 hydrocarbons which' com-` Prises subjecting the mixturein a polymerization step to conditions of elevated temperaturewithin the range of 300 l'. to 900 F. and superatmospheric pressure, within fthe range or atmospheric pressure' to about 500 pounds per square inch which result in dimerization of butadiene in the presence of other Ci hydrocarbons to -the dimer thereof asthe principal reaction occurring. separating the dimer from the eilluent of the polymer-nation step. subiectins the dimer, urs depolymerization step to conditions of elevated temventures in the range o! 900 l". to 1300 F. and in the presence of suiiicient steam v.to maintain low partiall pressure of the dimer which result in depolyr'nerization of dimer to monomeric butadiene,

fractionating the eiiluent of the depolymeris'ation step in a fractionation step to form a fraction containing the monomeric butadiene and atrae# tion containing the dimer eiliuent oi the depolymerization step. and recycling the dimer from the fractionation step to the depolymerisation 3WD- 5. The process which comprisesrubiecting the dimer of `butadiene to a temperature within the range of about 4900 Il'. to about 1300 IIL-in admixture with suiiicient steam to maintain the partial pressure of said dimer within the range of 3 to 100 mm. eifecting depolymerisation of said dimer as the principal reaction oi' the process.

8. The process which comprises subjecting the dimer of butadiene to a temperature within the ranae of about 900' l". to about i300 Ein admixture with suiiicient steam to maintain the partialpressureo'fsaiddimerwithintherangeof to 100mm. and in the presence of a magnesium merisation of said dimer as the o( the m anoressia. gamma..

recycling the dimer to the' 

